Cosmetic preparation

ABSTRACT

An aqueous-based preparation for application to the skin or skin appendages, which contains a mixture of at least two aqueous dispersions of film-forming polymers of which one is a polyurethane-based polymer and the other is an acrylate-based polymer, and optionally conventional constituents, wherein the preparation is of a viscosity in the range of between 0.02 and 3.8 Pa.s measured at 25° C. and with 200 s −1 .

BACKGROUND OF THE INVENTION

The invention concerns a preparation for application to the skin or skinappendages and the use thereof, a process for the production thereof anda device for the application thereof.

The preparation according to the invention can be used for decorativepurposes, for making up the skin, the semi-mucous membranes or regionsof the skin in the proximity of mucous membranes. It can also be appliedto skin appendages. Thus there are products which can be applied to skinappendages such as hair, eyelashes and eyebrows or also the artificialreproductions thereof in order to impart desired properties thereto. Itis known for keratin fibers to be covered with a coating which impartsfullness and volume, an attractive shape and/or also color. For exampleeyelashes can be provided with a colored coating, which emphasizes them,shapes them and possibly also makes them longer. It is further known forhair to be provided with a coating which smoothes the hair, gives volumethereto or possibly also colors individual strands.

Preparations for making up the skin or the semi-mucous membranes aregenerally known in the form of pencils, in the form of pastes which arecast into small metal pots, in the form of soft pastes or in the form ofloose or pressed powders. Pencils or pastes are generally in water-freeform as mixtures of vegetable, animal or synthetic oils, fats and waxes,in which there is dispersed a powder paste comprising pigments which areallowed for cosmetics, pearl gloss agents and fillers such as talc,kaolin or amorphous silicon dioxide. Loose or pressed powders generallycomprise mixtures of pigments which are allowed for cosmetics, pearlgloss agents and fillers which can be put into a handleable or workableform by means of a binding agent on an oil base or in the form of anemulsion.

All those preparations suffer from the disadvantage that they onlyinadequately adhere to the location where they are applied and can beeasily transferred onto other materials such as crockery, cutlery,glass, textiles or skin. That gives rise to the need for thosepreparations to be repeatedly applied. As oils spread on the skin and onsemi-mucous membranes and in addition also involve differing spreadingcapability, constituents of those preparations, in particular pigments,can bleed out of lipsticks into the fine creases in the skin around thelips and thus produce structures which are a nuisance because they areunattractive. Those effects can be provoked or boosted by the sebum ofthe skin and by perspiration. Eye-shadows in powder form for example canmigrate in particular into the creases in the eyelid due to the movementof the lids and due to the effect of sebum, and as a result can producestrip-shaped structures.

The attempt has been made since 1978 to produce wax-based cosmeticpencils, in particular those with leads which are cast into injectablecases, on pigmented wax mixtures which contained a marked proportion ofvolatile oils, preferably volatile silicone oils such as cyclomethiconesor hydrocarbons such as isoparaffins or mixtures thereof. Thosepreparations were at times also improved in respect of their propertiesof use by additions of non-volatile silicones such as alkyldimethiconeor phenyl trimethicone. Particularly when using micas coated with metaloxides, it was possible to achieve very soft and malleable andhigh-gloss preparations with very good adhesion capability, which werevery well accepted on the market by the consumer.

A disadvantage in this respect however was the content of volatileconstituents, which on the one hand required very good sealing of thepencil materials used such as casing, closure cap and end cap, and whichon the other hand sometimes resulted in consumer complaints if suchcosmetic pencils were stored open without a closure cap for a prolongedperiod of time because they then shrink because of evaporation of thevolatile constituent and harden to the point of no longer being suitablefor use. On the other hand female consumers felt water-free preparationsbased on oils, fats and waxes as forming an unpleasant film on the skinor on semi-mucous membranes, particularly if that preparation wasapplied in a relatively thick layer.

The attempt has therefore already been made to produce aqueous oraqueous-alcoholic preparations in the form of polymer-bearingdispersions which no longer contained any oils, fats or waxes, whichwere intended to no longer suffer from the above-discussed disadvantagesand which formed elastic and more or less water-resistant films on theskin or on semi-mucous membranes. Thus for example G. A. Nowak, in “Diekosmetischen Präparate”, 1st edition, 1969, pages 588 and 589, describesvarious compositions of eyeliners and liquid makeup which are based onsynthetic film-forming agents such as polyvinyl pyrrolidone (PVP) orcarboxymethylcellulose or natural film-forming agents such as shellac,tragacanth or gum arabic. On page 441 G. A. Nowak describes lipsticksbased on solvents such as ethyl alcohol or isopropanol which asfilm-forming agents contain ethyl cellulose, cellulose acetate, shellac,methyl abietate or PVP. Such preparations however have evidently notproved worthwhile in practice because of the content of solvents. EP-A 0793 957 describes a composition which can be applied to the skin, thesemi-mucous membranes or the membranes, which contains an aqueousdispersion of particles of a film-forming polymer which, on a carrier,forms a film of a hardness of less than 110 (determined in accordancewith the standard NF-T-30-016). The examples each describe an eyelinerand a lip rouge based on polyurethane dispersions. Those compositionsare intended to form a film which adheres well to the substrate andwhich is soft and flexible, which follows the movement of the skin anddoes not crack and which does not become detached. Those compositionsare intended not to bleed on the skin and not to be transferred ontoother materials.

In addition EP-A 1 010 418 discloses a wax-free gel composition whichcontains polyurethane polymers as film-forming agents. That compositionis used as mascara and is intended to adhere to the eyelashes for longerthan a day. To adjust the viscosity, preferably a pyrogenic silicic acidis used for those compositions, but the silicic acid, particularly whenapplied more heavily results in the material flaking off.

EP-A 1 249 225 also describes a wax-free gel composition which is saidto be water-resistant and which is said to adhere for more than twodays. That composition is intended to be used in particular as acoloring agent for hair, eyelashes and eyebrows and after applicationand drying is intended to form a smooth coating. It will be noted thatthere is the disadvantage here that the pyrogenic silicic acid containedin the composition severely thickens it, even when present in arelatively low level of concentration, and causes the dried film toappear dull. As in addition it is not hydrophobized, it promotes waterabsorption on the part of the film and thus reduces the water-resistanceand thus its durability.

In addition U.S. Pat. No. 6,458,390 describes a makeup composition whichcontains iron oxide pigments and film-forming agents and which is saidto adhere for a long time. It will be noted that, for this composition,it is necessary to use a specific silicone acrylate copolymer dissolvedin a volatile solvent. In comparison the invention involves using anaqueous dispersion. Aqueous-based products can contain the constituentseither in dissolved or dispersed form, in the latter case it isnecessary to take care to ensure that, when constituents such as forexample pigments are not dissolved, they do not settle with time andthus result in products which are unusable.

In addition with all these products there is the requirement that, afterthey have been applied, they remain in position and do not run, comeoff, flake away or bleed out. In the ideal situation the products shouldbe resistant even when bathing or showering, that is to say upon cominginto contact with water, possibly even in connection with shampoos,shower preparations or soap. Specifically for eyelash mascara it isdesirable for it to remain on the eyelashes, even when it comes intocontact with water. In addition it should not come off when rubbed andin particular should not color the area around the eye. In addition thecoating should be such that it retains the constituents thereof so thatportions thereof cannot bleed away therefrom and color the surroundingarea.

Therefore the object of the present invention was to provide apreparation, in particular a cosmetic preparation, which can be appliedfor decorative purposes for makeup to the skin, to semi-mucous membranesand/or in the proximity of semi-mucous membranes. That is intended todenote in particular application to the skin of the face and/or thebody, to the lips and to the eyelids and to lid edges. In particular liprouge, blusher, makeup, eye-shadow, lipliner, eyeliner, concealer andbody paints such as so-called temporary tattoos or Mehndi decoration areintended to be interpreted as preparations for makeup.

A further object of the invention was to provide a cosmetic preparationwhich can be applied to skin appendages and which adheres there for aprolonged period of time, for example more than 8 hours and inparticular more than a day, remaining at the location at which it wasapplied, without being removed by water, perspiration or contact witharticles, but which on the other hand can also be easily removed again.A further object of the invention was to provide a wax-free preparationwhich provides a durable and glossy coating. In addition the inventionaimed to provide a preparation which can be easily applied and whichenjoys a high level of storage stability.

SUMMARY OF THE INVENTION

In accordance with the invention to attain that object a mixture is usedcomprising at least two aqueous dispersions of film-forming polymers,which leads to better adhesion and longer storage capability.

Accordingly, the aqueous-based preparation according to the inventionfor application to the skin or skin appendages contains a mixture of atleast two aqueous dispersions of film-forming polymers of which one is apolyurethane-based polymer and the other is an acrylic-based polymer,and optionally conventional constituents. In a preferred embodimentwhich is particularly suitable for application to the skin appendagesthe preparation is of a viscosity in the range of between 0.02 and 3.8Pa·s, measured at 25° C. and with 200 s⁻¹.

DETAILED DESCRIPTION

The preparation according to the invention is in the form of an aqueousdispersion which after application dries to provide a water-resistantfilm and which enjoys excellent adhesion to the location at which it wasapplied. That film is elastic and stretchable and can therefore followthe movements of the skin and semi-mucous membranes or the hair. Inaddition, upon drying, it neither contracts nor does it shrink to aconsiderable degree so that it does not produce any feeling of pullingon the skin or the lips and also does not flake off. It also does notbecome cracked or grainy and it is so elastic and durable that it doesnot become detached from the edge of the application or even as awhole—rather it remains “like a second skin” at the location at which itwas applied. Its constituents do not move, not even under the influenceof sebum or perspiration, and its constituents also cannot betransferred onto other materials. In general the film already exhibits ahigh surface gloss and high reflection capability upon drying, but atthe latest after complete drying. After complete drying the film is sostable that it is not detrimentally altered by a possible secondapplication of the preparation. In no way may the dried film stick orgive a sticky feel.

If the preparation according to the invention contains coloring agents,they must involve such grain sizes, surface properties and forms thatthe coloring agents do not detrimentally influence film formationalthough—so-to-speak as “foreign bodies”—they interfere with theformation of the film. The following can be mentioned as coloring agentswhich are suitable for cosmetic preparations: inorganic pigments, forexample yellow, red or black iron oxides, ultramarine, chromium oxidegreen, chromium hydroxide green, carbon black and/or optionally organicpigments, lakes of organic coloring agents, metal powders in flake form,for example passivated aluminum, brass, bronze, copper, silver or gold,mica, mica coated with metal oxides, for example with titanium dioxide,iron oxides, chromium oxide, chromium hydroxide, preparations in flakeform based on silicon dioxide, aluminum oxide or glass which canoptionally also be coated with metal oxides, for example titaniumdioxide, iron oxides, chromium oxide and chromium hydroxides andmixtures thereof. In that respect the specified synthetic materials inflake form have the advantage that they can be produced in a uniformlayer thickness and can already be subjected to further processing moreeasily at the preliminary supplier.

In accordance with the invention there is provided a composition whichcan be very easily applied and, as soon as it has been applied, adheresto the position of application for a long time without adverselychanging, being transferred onto other articles, bleeding into adjacentregions or running or flaking off. In addition in spite of its lowviscosity the composition can also be stored for a very long period oftime without constituents settling. The coating or film obtained withthe composition according to the invention has the gloss which isdesirable for cosmetics.

All these desirable and advantageous properties are achieved if anaqueous composition involves the use of at least one dispersion of apolyurethane polymer in combination with at least one dispersion of anacrylic polymer. For that purpose the dispersions are used in suchproportions that it is possible to obtain a preparation having aviscosity in the desired range. Surprisingly it was found that acombination of those two constituents provides that it is possible toform a stable product of low viscosity, the adhesion of which to skinand skin appendages is highly advantageous. Those advantageousproperties are achieved only if at least one representative of each ofthe two polymer classes specified is included. In addition thoseadvantageous properties are achieved without the preparation having tocontain a wax. A wax can admittedly be added to that preparation, but itis not necessary to achieve the desired properties and it is thereforenot preferred.

As an essential feature of the preparation according to the inventiontherefore the content of an aqueous dispersion of at least onepolycondensate is selected from anion-active, cation-active,non-ionogenic or amphoteric polyurethane polymers or copolymers. In thatrespect the polyurethane can advantageously be selected from the groupof polyester polyurethanes, polyether polyurethanes, polyurethanepolyvinyl pyrrolidones, acrylic polyurethanes and silicone-bearingpolyurethanes as well as mixtures thereof.

The polyurethane is present in the aqueous phase in the form ofparticles, the size thereof preferably being in a range of between 10and 1,000 nm, particularly preferably between 15 and 300 nm and inparticular 30 and 100 nm.

All polyurethane dispersions which form a film after application aresuitable. Polyurethane polymers of that kind are known to the manskilled in the art. Examples that may be mentioned are polyesterpolyurethanes as are offered for example by Noveon (formerly BFGoodrich) under the name Avalure, for example Avalure UR-425, AvalureUR-430, Avalure UR-405 and Avalure UR-410, or also products as arefurnished by Zeneca under the name Neorez. The preferred polyurethanepolymer is one which is identified by the CTFA designation aspolyurethane-2.

The polyurethane polymer is used in the form of an aqueous dispersion.Preferably a dispersion of the polymer with a proportion of polymer ofbetween 10 and 80%, preferably between 30 and 60% in water is used. Alsosuitable are mixtures of the above-listed polyurethane polymers, inparticular mixtures of polyester polyurethanes and polyetherpolyurethanes or also mixtures of polyurethane polymers with polyureas,siliconyl acrylates, PEG/PPG-25/25 and/or dimethicone/acrylatescopolymer.

The proportion of the aqueous polyurethane dispersion in the overallcomposition should be in a range of between 1 and 60%, preferablybetween 15 and 50%. All percentages in this description, the Examplesand the claims always relate to weight unless otherwise stated. In thecase of the film which is formed, the polyurethane composition providesinter alia for water-resistance. Below a proportion of 1% the desiredeffect of the polymer no longer occurs. With more than 60% adjustment ofviscosity and the incorporation of coloring agents becomes moredifficult.

The second essential component of the composition according to theinvention is at least one acrylic-based polymer which provides foradhesion of the composition, gloss and resistance to being rubbed off.In general this involves a polymer which is obtained by radicalpolymerization and which is preferably an acrylates copolymer or acrylicand/or vinyl polymer and/or acrylic and/or vinyl copolymer. Thosepolymers are obtained in particular by radical polymerization ofsuitable monomers, preferably by way of emulsion polymerization. Inprinciple it is also possible for the polymers obtained by radicalpolymerization to be dissolved in a suitable solvent and for thesolution to be re-used. Suitable monomers that may be mentioned areacrylic acid, crotonic acid, maleic acid anhydride or methacrylic acid.Acrylic polymers and copolymers however may also be obtained bypolymerization or copolymerization of monomers which are selected forexample from monomers such as methyl acrylate, ethyl acrylate, butylacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate,butyl acrylamide, ethyl hexylacrylamide and the like.

Acrylic polymers are also used as aqueous dispersions, the particle sizeof which is in the same range as in the case of the polyurethanepolymer. As the acrylic polymer or acrylates copolymer, it is possibleto use both aryl acrylate copolymers and also alkyl acrylate copolymers,wherein in the latter case the alkyl component can have between 1 and 30C-atoms. The acrylates copolymer is a polymer which is preferablyobtained by polarization of at least one monomer which includes anethylenically unsaturated bond and is selected from α,β-ethylenicallyunsaturated carboxylic acids, α,β-ethylenically unsaturated carboxylicacid esters and α,β-ethylenically unsaturated carboxylic acid amides andcombinations of two or more of those monomers. Preferably acrylic acid,methacrylic acid and esters and amides thereof as well as crotonic acid,maleic acid and itaconic acid are used as the α,β-ethylenicallyunsaturated carboxylic acids. (Meth)acrylic acid and crotonic acid arepreferably used. Particularly preferred are acrylic acid and methacrylicacid and esters thereof.

The α,β-ethylenically unsaturated carboxylic acid esters considered arein particular (meth)acrylic acid esters in which the ester component isa C₁-C₃₀ alkyl residue or C₆-C₁₀ aryl residue. In that case the alkyland aryl components respectively can be additionally substituted, forexample with hydroxy residues. Preferred acrylates which can be usedinclude methyl methacrylate, ethyl methacrylate, butyl methacrylate,isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylateand cyclohexyl methacrylate. Preferred aryl methacrylates which can beused include benzyl acrylate and phenyl acrylate. Copolymers of styreneand (meth)acrylic acid (esters) are particularly suitable.

It is moreover also possible to use carboxylic acid amides. Mention maypreferably be made of N-alkyl or N-aryl(meth)acrylamides in which thealkyl component can have between 2 and 15 C-atoms or in which the arylcomponent can have between 6 and 10 C-atoms. N-ethyl acrylamide,N-t-butyl acrylamide, N-t-octyl acrylamide and N-undecyl acrylamide canbe preferably mentioned here.

In addition it is also possible to use copolymers of the specifiedmonomers with other olefinically unsaturated monomers. Examples in thisrespect are acrylic copolymers which were obtained by copolymerizationof acrylic acid or methacrylic acid with monomers such as butadiene,styrene or vinyl esters such as vinyl acetate or vinyl benzoate.Preferably copolymers are used which are obtained by copolymerization ofacrylic acid or methacrylic acid with styrene or vinyl compounds.

The acrylates copolymer is used in the form of an aqueous dispersion,wherein the aqueous dispersion contains the copolymer in a proportion ofbetween 20 and 70%, particularly preferably between 25 and 40%. Theproportion of the acrylates copolymer or the aqueous dispersion of theacrylates copolymer in relation to the overall composition is between 1and 60%, in each case with respect to the weight of the overallcomposition, and preferably between 15 and 35%. The desired resistanceto being rubbed off is not achieved below a proportion of 1%. When aproportion of more than 60% is involved the swelling capability of thedried film is increased and thus there is a reduction in its waterresistance, which leads to poor properties of use. In addition there isa considerable increase in the degree of difficulty in working incoloring agents.

In a preferred embodiment of the invention the acrylic component used isa mixture of at least two different acrylic-based polymers of which oneis preferably an acrylates copolymer and the other a copolymer ofacrylic acid/methacrylic acid monomers and ethylenically unsaturatedaryl monomers. Preferably the latter acrylic polymer is astyrene-bearing acrylates copolymer. In that respect styrene acrylatesammonium methacrylate copolymer is preferably used.

That component is also preferably used in the form of an aqueousdispersion, the dispersion generally containing between 30 and 50% ofpolymer in water. The proportion of that specific aryl/acrylatecopolymer in relation to the overall composition is between 1 and 60%,wherein a proportion in the range of between 15 and 35% and inparticular between 20 and 30% is particularly preferred.

In an embodiment which is particularly suitable for application to skinappendages, the aqueous polymer dispersions form between 50 and 90%,preferably between 55 and 75%, of the overall composition. In that casepreferably a polyurethane dispersion, an acrylates copolymer dispersionand a styrene/acrylic dispersion are used. That combination isparticularly preferably used in such proportions that the polymerproportion is formed for between about 35 and 55% of polyurethane, forbetween about 15 and 25% of acrylates copolymer dispersion and thebalance styrene/acrylic dispersion.

In order to achieve particularly good properties the polymers arepreferably so selected that between 30 and 60% of the polymerdispersions of copolymers or polymers which are water-resistant in thedried condition have a glass transition temperature below 10° C.Particularly preferably, with between 5 and 30% of one or more of thedispersions of statistical or block copolymers, a block or portion inthe dried condition has a glass transition temperature of more than 30°C.

It was also found that particularly advantageous results are achieved ifall film-forming polymers have a minimum film-forming temperature below30° C. and preferably below ambient temperature.

The preparation according to the invention, in addition to theabove-specified polymer components, may contain still further polymersas long as they are compatible and do not adversely affect theproperties of the components according to the invention. Thus they mayalso contain so-called hybrid polymers which can be obtained bycopolymerization in the form of acrylic or vinyl polymers with siliconesegments or silicone groups. Polycondensates with silicone segments orsilicone groups are also known and commercially available.

Polyesters, polyester amides or polyamides are also suitable. Polyesterscan be obtained using the methods known to the man skilled in therelevant art, by polycondensation of aliphatic or aromatic dicarboxylicacids with aliphatic or aromatic diols or polyvalent alcohols.

Mention may be made here by way of example of polycondensates comprisingadipic acid, succinic acid, glutaric acid, sebacic acid, terephthalicacid or isoterephthalic acid with diols such as ethylene glycol,diethylene glycol, propylene glycol or polyvalent alcohols such asglycerin, trimethylol propane, pentaerythritol, mannitol, sorbitol orxylitol or polymer soft segments such as poly-THF. Polyester amides areobtained in a corresponding manner by the polycondensation ofdicarboxylic acids with diamines or amino alcohols.

The following will be mentioned just by way of example as suitablenatural polymers: shellac, dammar resin, copal, elemi, tragacanth, gumarabic, xanthane or cellulose derivatives which can optionally bechemically modified, and mixtures thereof.

A further essential feature of the composition according to theinvention is viscosity which is in a range of between 0.02 and 3.8 Pa·s,measured at 25° C. and 200 s⁻¹. Viscosity can be measured in per seknown manner using a rheometer. The measurement procedure is suitablyeffected with a rheometer of type BOHLIN CVOR (plate/plate measuringsystem) at 25° C. and at a shearing rate of 200 s-1 withoutpre-shearing. In this respect attention is additionally directed to thestandard DIN 53018, Part 1 and Part 2.

It was surprisingly found that the composition according to theinvention, in spite of the low viscosity, is very durable and can bestored over a long period and by virtue of its structure can also holdparticulate constituents in dispersion so that no settlement of thecoloring agents or separation into their constituent parts occurs.

Besides the above-described film-forming polymers, depending on thedesired properties and the respective area of use, the compositionaccording to the invention may contain further conventionalconstituents.

If the composition according to the invention is intended for coloring,for example for dyeing hair including eyelashes and/or eyebrows, orhowever as decorative eye cosmetics, for example as eyeliner, it furthercontains coloring agents. Coloring agents for compositions of this kindare known per se and those which are suitable for cosmetics can also beused for the material according to the invention.

For coloring the preparation according to the invention it is possibleto use inorganic pigments such as titanium dioxide, zinc oxide, ironoxides, chromium oxide green, chromium hydroxide green, ultramarine,carbon black, organic pigments such as carmine and its salts orphthalocyanine, mica, mica coated with metal oxides such as titaniumdioxide, iron oxide or chromium oxide, bismuth oxychloride or bismuthoxychloride coated with metal oxides, preparations in flake form basedon silicon dioxide, aluminum oxide or glass, which can optionally alsobe coated with metal oxides, for example titanium dioxide, iron oxides,chromium oxide, chromium hydroxide, metal powders in flake form such aspassivated aluminum, bronze, brass, copper, silver, gold, barium,aluminum, strontium, calcium or zirconium lakes of organic dyestuffs ormixtures thereof. When selecting the respectively appropriate coloringagent, consideration should also be given to the national or regionallegislation relating to the manufacture of cosmetics as in manycountries coloring agents which come into contact with the mucousmembranes of the eye must be approved. In Germany for example approvalfor coloring agents is regulated by Appendix 3 to Regulation 3 of theCosmetics Regulations.

Both organic soluble dyestuffs and also pigments can be used forcoloring keratinic fibers, in particular eyelashes, eyebrows and hair.Pigments are preferred for the composition according to the invention.Both normal pigments and coated pigments can be used. The pigments arepreferably of a small particle size, preferably in a range of between 20nm and 150 μm. For that purpose the pigments are finely ground in theusual manner or possibly used in micronized form.

If the composition according to the invention is to be used for coloringeyelashes and eyebrows, for example black iron oxide or ultramarine blueare suitable coloring agents as pigments. The proportion of the pigmentdepends on the desired coloration and suitable amounts are known per seto the man skilled in the art. For example a proportion of between 0 and30%, in particular between 5 and 25%, is to be considered for thecomposition according to the invention. For specific dyestuffs withwhich particular effects are to be achieved however proportions outsidethose ranges are optionally also possible.

The storability of the products according to the invention can beimproved by using preferably pigments with a hydrophobic, physically orchemically adhering coating. Coatings for pigments are known per se anddo not need to be described in greater detail here. Suitable examplesare silicone-bearing coatings with dimethicone or other silicones orcoatings with titanium triisostearate. The use of coated pigmentsaffords the further advantage that wetting or swelling of the filmformed, upon contact with water, is minimized. That further enhances thedurability and resistance of the film formed. Even if the film swellssomewhat upon coming into contact with water, it remains completelyintact and stable if it is not exposed to mechanical friction in theswollen condition.

When using strongly hydrophobically coated pigments it is recommendedthat a surface-active substance also be added to the composition,optionally in combination with a polymeric wetting agent. Suchsurface-active substances and wetting agents contribute to the watercompatibility of the particles.

Examples of suitable surface-active agents that may be mentioned arelow-molecular tensides such as sarcosinates, non-ionic and/oranion-active tensides such as PEG-modified fatty acids and fattyalcohols, sodium laureth sulfate, solubilizers as are also conventionalfor the compatibilisation of UV substances, and/or ester oils.

If they are present the low-molecular tensides are used preferably in aproportion of between 0.1 and 3% in each case with respect to the weightof the overall composition.

Suitable polymeric wetting agents are for example silicone tensides andamphiphilic siliconyl acrylates and PVP derivatives, for exampleVP/eicosene and VP/hexadecane copolymer, fluorotensides, cholesterolesters, lecithin and acrylate copolymers, for example an acrylate blockcopolymer and other known polymer tensides. An acryl-bearing wettingagent is particularly preferably used as the polymeric wetting agent inorder to improve compatibility. If present the polymeric wetting agentis appropriately used in a proportion of between 0.05 and 5%, preferablybetween 0.1 and 3%. In a preferred embodiment a non-ionogenic wettingagent, in particular a dimethicone copolyol or a non-ionogenic polymericwetting agent such as for example an acrylate or polyethylene blockcopolymer is used in a small amount, preferably between 0.05 and 3% byweight, quite particularly preferably between 0.3 and 1.5% by weight.That provides that the coloring agent particles on the one hand are wellwetted and on the other hand are bound into the polymer structure bymolecular interactions. At the same time that provides that, upondrying, the film is particularly smooth and thereby affords a high levelof surface gloss. That can also be achieved by the use of polymersegments with a reflection capability which is known to be good, andwith a relatively high glass transition temperature T_(g), such as forexample polystyrene.

In a preferred embodiment of the preparation according to the inventionwhich is pigmented preferably thickening agent which provides for stillbetter storage stability is used together with the pigments. As at thesame time however the material obtained should not become crumbly butmust be such that it can be applied smoothly, not all known thickenersare suitable for that purpose. In particular pyrogenic silicic acid isunsuitable as it results in the composition crumbling away after it hasbeen applied. In addition the preparation according to the inventionshould be of such a low viscosity that it is free-flowing and thereforecan also be stored in vessels of the most widely varying geometrywithout a problem arising in terms of removal therefrom. It wassurprisingly found that a low-viscosity preparation can be obtained if athickener mixture is used, which contains at least one inorganiclaminate silicate combined with a xanthane gum. Suitable mixtures arethose comprising natural and synthetic as well as modifiedpolysaccharides, mineral and modified mineral thickeners, silicatethickeners, celluloses and modified celluloses, non-ionic associativethickeners, copolymer thickeners such as hydroxyethyl acrylate/sodiumacryloyl dimethyltaurate copolymer, sodium acrylate acryloyldimethyltaurate copolymer, sodium acrylate/acryloyl dimethyltauratecopolymer, and VP/dimethiconyl acrylate/polycarbamoyl/polyglycol ester.Particularly good properties are achieved if a mixture is usedcomprising a larger proportion of a hydrocolloid or vegetable gum, forexample xanthane gum, a smaller proportion of a silicatic thickener anda small proportion of a polysaccharide, in particular cellulose, whichcan optionally also be chemically modified. By way of example referencemay be made to a mixture comprising between 40 and 70% xanthane gum,between 10 and 40% of mineral thickener and the balance cellulose orcellulose derivative. The thickener used is particularly preferably amixture of cellulose, silicate and xanthane gum in a ratio in the rangeof between 1:1:4 and 1:2:6.

The thickener mixture can be added in a proportion of up to 20%,depending on the respectively desired viscosity. In general termsproportions in the range of between 0.2 and 5% have proven to besuitable, in each case in relation to the weight of the overallcomposition. If a lower viscosity is wanted it will be appreciated thatthe thickener proportion can be used in the lower range while theproportion of thickener is increased if the viscosity is to beincreased.

The thickener mixture used according to the invention stabilizes thepigments and thus substantially prevents the pigments from settling. Inthat way the pigments remain homogenously distributed even when storedover a relatively long period of time and do not have to be re-dispersedby being shaken up prior to each use.

On the other hand the low viscosity which can be achieved in spite ofthe use of the thickener mixture provides that the material is notapplied on the eyelash and nonetheless provides for good colorationthereof. A disadvantage with a relatively thick application is that inthat situation, when drying occurs, stresses are produced which have theresult that the material flakes off after some time. In contrast thecomposition according to the invention provides a coating which remainsdurably at the location of application for a long period of time, byvirtue of its elasticity and its uniform layer thickness.

In an embodiment the preparation according to the invention may alsocontain one or more conventional and per se known sun protection agentsor UV-absorbent agents in order to protect skin or hair from solarradiation. Frequently this embodiment is used without a pigmentaddition. The sun protection agents are used in the amounts which areconventional for cosmetics.

If a preservation effect is wanted for the composition according to theinvention, it is possible for that purpose to use all common preservingagents, inter alia carbamates, for example iodine propinyl butylcarbamate. The use of those preserving agents is implemented up to theamounts which are allowed by statute, as are set out for example inGermany by Appendix 6 to Regulation 3a of the Cosmetics Regulations inthe respectively applicable wording.

In order further to improve the rheological properties of thecomposition according to the invention and application of thecomposition it is optionally also possible to use co-solvents, that isto say water-miscible solvents. Suitable substances here are for examplemonovalent and/or polyvalent alcohols with between 2 and 20 carbonatoms, esters and ethers thereof, liquid compounds which are misciblewith water or which are easily dispersible in water such as for exampleN-methyl pyrrolidone, dimethyl acetamide, glycerin, diglycerin,triglycerin, butylene glycol, hexane triol, propylene glycol,dipropylene glycol, hexylene glycols, mixtures of dimethicone copolymerand caprylic/capric triglyceride or other suitable silicone tensides, aswell as solutions of sold substances which are easily soluble in waterand which serve as agents for keeping the material moist but not asco-solvents, such as for example urea, xylitol, inositol, maltitol,sorbitol, mannitol, glucose, fructose, sucrose, lactose, trehalose,diglycet-7-malate, glyceryl dimaltodextrin, sorbityl silanediol, as wellas amino acids or nitrogen-bearing compounds such as acetyl arginine,amidinoproline, betaine, chitosan lauroyl glycinate, diglycol guanidinesuccinate, derivatives of guanidine acetate and mixtures thereof.Preferably the co-solvents used are polyvalent alcohols which at thesame time also serve as agents for keeping the material moist. Theco-solvent is usually contained in the material in a proportion ofbetween 0 and 5%.

The film-forming polymers used according to the invention have a glasstransition temperature in a range which causes a soft and elastic filmto be produced, even without a plasticiser. If however the softness andelasticity are to be increased still further or if running of thematerial is to be further promoted, it is also possible to add aplasticiser which is known for cosmetic materials. Suitable materials inthis respect are both low-molecular and also higher-molecularplasticisers which are optionally used solubilized or dissolved in aco-solvent. Silicone tensides, but also short-chain ester oils, areconsidered as being suitable here. The hardness of the film formed fromthe preparation according to the invention can also be influenced by theaddition of benzoyl benzoate, tributyl citrate, trihydroxy propylcitrate, or laureth-2-benzoate.

If present the plasticisers can be used in per se known manner, forexample in a proportion of between 0 and 5%.

In order to prevent foaming of the composition during manufacture or inuse—for example in the case of the eyebrow mascara due to the “airpumping effect” when the applicator is pulled out of and re-introducedinto the container—, which can be disadvantageous when applying thecomposition, it is possible to add per se known anti-foam agents in asmall amount. Examples in that respect are silicone compounds as arealso used for other cosmetic compositions. Usually a silicone compoundof that kind is used in the form of an emulsion in a proportion ofbetween about 0 and 5%, preferably between 0.1 and 1%.

When the applied material is to be removed again that can be effected ina simple manner by water being applied to the applied film at relativelyhigh temperature, for example a temperature above 25° C., preferablybetween 30 and 38° C., and by the film then being removed bymechanically rubbing, for example with a cotton wool pad.

The preparation according to the invention can be produced in per seknown manner. In order to obtain a particularly smooth and homogenousmaterial which can be well applied, production is preferably effected bya procedure whereby firstly the polymer dispersions are prepared andheated to an elevated temperature, preferably in the range of between 45and 60° C.

If a thickener mixture is used, it is preferably pre-dispersed in aco-solvent which can be mixed in any desired manner with water but whichis different from water, for example a polyvalent alcohol, glycerin orester oil. Both mixtures are then mixed together and the furtherconstituents are added in the usual manner. The coloring agents can thenbe worked into the homogenous dispersion and uniformly distributedtherein.

That material can now be readily introduced into the device from whichthe composition is to be delivered. The composition according to theinvention is so stable that, even without agitation, it does not settleor separate into its constituent parts. The composition can possiblyalso be introduced while still hot immediately after manufacture, intothe containers provided for it.

In rare cases, during the cooling operation, some water may be depositedat the surface, which however can be homogenously distributed again bysimply stirring it in. As the viscosity of the composition according tothe invention is low, it can also be filled into the containers intendedfor it in the cold condition, which is advantageous in terms ofpreserving the structure of the material.

If desired, after completion of the composition, adjuvants such asplasticisers, gloss-imparting agents, run adjuvants and so forth canalso be added to the composition.

The composition according to the invention can be used for the treatmentof skin and skin appendages. In particular the composition according tothe invention is suitable on the one hand for making up the eyes and onthe other hand for the treatment of keratinic material, in particulareyelashes, eyebrows and hair.

A further subject of the invention is therefore use of the preparationaccording to the invention for making up eyes, preferably the eyelids,eyelid edges, eyelashes and eyebrows.

A further subject of the invention is use of the preparation accordingto the invention for the treatment of keratinic material, in particularhair, eyelashes and eyebrows, both in the natural condition and also thesynthetic imitations thereof.

Preferably the preparation according to the invention is used to providekeratinic material with a coating, in particular a coloring coating.That coating is durable over the long term and is maintained even uponcoming into contact with water. The coloring is maintained for up to 4days. If desired the coating can be removed again at any time byapplying water, preferably at relatively high temperature, and removingthe coating by mechanical rubbing after a few minutes.

If the preparation according to the invention is used for application tokeratinic material, the application can preferably be implemented withan applicator system which includes a container and a removable elementfor closure thereof, wherein the closure element is preferably anapplication element, that is to say an applicator.

A further subject of the invention is therefore also a device forapplying a preparation, as described hereinbefore, which includes acontainer which can accommodate the preparation and a neck portion witha screwthread and seal, and an applicator element which at its one endforms a brush and at its other end a handle forming a closure cap,wherein the brush head is of a diameter in the range of between 5.5 and6.5 mm and a length in the range of between 12.5 and 17.5 mm and whereinthe bristles are arranged in a helical arrangement radially around acentral portion with a high number of turns.

In a preferred embodiment the applicator system has a container whichcontains the preparation according to the invention and which isprovided with a neck portion. The neck portion has an annular stripperor wiper. The element for closing the container carries an applicatorwhich has a stem and which at its first end is provided with a brush asthe applicator element and which at its second end is connected to ahandle. In the closed condition the closure element closes thecontainer, in which case the applicator mounted on the closure elementdips into the preparation. To apply the preparation the closure elementis pulled out, in which case the applicator moves over the annular wiperand in that operation wipes off excess material. The preparation canthen be applied with the brush. As the preparation according to theinvention is of an extremely low viscosity, it is possible for thecontainer to be designed in many different geometries, which is notpossible with the known applicator systems for mascara. Conventionalmascara is of a relatively high viscosity and therefore can only bestored in cylindrical containers into which the applicator can beintroduced in such a way that it can remove the material. As thepreparation according to the invention is of such a viscosity that thematerial is freely flowing, the preparation can also be introduced intomore bulbous or rounded vessels or vessels of any geometry.

In a preferred embodiment the applicator for applying the preparationsatisfies the following conditions so that application is homogenous andresistant. In the preferred embodiment the applicator is a brush withsoft bristles so that, upon repeated application, the bristles cannotdamage the layer which has already been applied and thereby make it opento attack by water. In addition the brush is briefly of large diameterso that individual parts of eyebrows can be specifically colored. In aparticularly preferred feature the brush used is of a diameter at thetip of between 5.5 and 6.5 mm, a length of between 12.5 and 17.5 mm withnylon as the fiber material measuring 2.5 mils. Particularly preferablya brush with a large number of turns is used.

In accordance with the invention there is provided a preparation whichcan be applied durably and resistantly to skin and skin appendages andwhich can remain thereon for a very long period of time. As soon as thepreparation has been applied to the desired part and has dried, whichrequires only a short period of time, it remains adhering to thelocation of application without transferring onto articles which comeinto contact therewith, without bleeding into near regions or crumblingoff. The preparation is therefore ideally suited for application tokeratinic material, in particular eyelashes, eyebrows and hair. Thepreparation can be applied to hair in order to impart thereto aprotective coating and at the same time body and life. In a preferredembodiment the preparation is provided with coloring agents and servesfor coloring the keratinic material.

The invention will be further described by means of the followingExamples without being restricted thereto.

EXAMPLE 1 Body Tattoo

% by wt. Isodecane acrylates copolymer 23.500 Aqua 19.400PPG-17/IPDI/DPMA copolymer 20.000 Acrylates copolymer 16.500 Propyleneglycol 3.500 Methyl eugenol PEG-8 dimethicone 2.200 Adipicacid/diethylene glycol glycerin crosspolymer 2.000 C12/C15 alkylbenzoate 1.000 Caprylic/capric triglyceride 1.000 Preservatives 0.750Dimethicone 0.150 Pigments 10.000

EXAMPLE 2 Lipliner

% by wt. Aqua 43.750 Polystyrene 16.000 Polyurethane-4 15.000 Glycerin6.000 Acrylates copolymer 4.000 Caprylic/capric triglyceride 3.000PEG-150/decyl alcohol/SMDI copolymer 1.000 Preservatives 0.750Dimethicone 0.500 Pigments 10.000

EXAMPLE 3 Eyeliner

% by wt. Acrylates copolymer 30.000 Aqua 24.450 Polystyrene 18.000Caprylic/capric triglyceride 5.000 Propylene glycol 2.500 Sorbitol 1.500Acetyl tributyl citrate 2.000 Preservatives 0.750 Sodiumcocoamphoacetate 0.500 PVP/dimethiconyl polycarbamyl/polyglycerol ester0.300 Pigments 15.000

EXAMPLE 4 Lip Rouge

% by wt. Aqua 44.250 Ammonium acrylates copolymer 15.000 Polyurethane-110.000 Dimethicone copolyol 6.000 Adipic acid/diethylene glycol/glycerincrosspolymer 5.000 Caprylic/capric triglyceride 4.000 Sodiumcocoamphoacetate 1.000 PEG-180/laureth-50/TMMG copolymer 1.000Dimethicone 1.000 Preservatives 0.750 Pigments 12.000

EXAMPLE 5 Eye-Shadow (Liquid)

% by wt. Aqua 32.750 Ammonium acrylates copolymer 15.000 Polyurethane-110.000 Adipic acid/diethylene glycol/glycerin crosspolymer 5.000Dimethicone copolyol 4.500 Caprylic/capric triglyceride 4.000 Propyleneglycol 3.000 Sorbitol 1.500 Sodium cocoamphoacetate 1.000PEG-180/laureth-50/TMMG copolymer 1.000 Preservatives 0.750 Dimethicone0.500 Pigments 21.000

COMPARATIVE EXAMPLE 6 Eyeliner

% by wt. Polyurethane-7 86.250 Dimethicone copolyol 4.000Caprylic/capric triglyceride 3.500 Glycerin 3.000 Preservatives 0.750Dimethicone 0.500 Pigments 2.000

A preparation produced in accordance with the Comparative Example—whichis not in accordance with the invention—has too little covering power,applies irregularly and fails in the preservation loading test—in spiteof an apparently sufficient amount of preserving agent which correspondsto the content in the Examples according to the invention.

EXAMPLE 7 Eyelash Mascara

% by wt. Water q.s. 100 Dicaprylyl maleate 0.50 Preserving agent 0.60Hydrophobically modified pigment 10.0 VP/hexadecane copolymer 0.30Sorbitol 1.50 Acrylates copolymer 20.00 Styrene/acrylates copolymer12.00 Polyurethane-2 28.00 Caprylic/capric triglyceride 1.00 Trimethylsiloxyamodimethicone 1.00 Anti-foaming agent emulsion 0.40Butane-1,4-diol 3.00 Xanthane gum 0.40 Bentonite 0.25 Gellan gum 0.08

EXAMPLE 8 Eyebrow Mascara

% wt. by q.s. 100 Laureth-2-benzoate 0.70 Preserving agent 0.70Hydrophobically modified pigment 8.00 Hydrolized wheatprotein/dimethicone copolyol acetate 0.40 Sorbitol (aqueous solution)1.50 Styrene/VP-copolymer (aqueous solution) 6.00 Ammonium acrylatescopolymer (aqueous solution) 25.00 PPG 17/IPDI/DMPA-copolymer (aqueoussolution) 30.00 Caprylic/capric triglyceride 1.00 Glycerin 1.00Bis-PEG/PPG-20/20 dimethicone 1.00 Anti-foaming agent (aqueous emulsion)0.40 Propane-1,3-diol 3.50 Hydroxypropyl cellulose 0.11 Xanthane gum0.30 Hectorite 0.15

The foregoing constituents are used to produce an eyebrow mascara by aprocedure whereby the acrylate copolymer dispersion and the polyurethanedispersion are provided and preheated to between 50 and 55° C. and thenthe further ingredients are added. The mixture is stirred until there ishomogenous material. The material can then be introduced into acontainer for accommodating it, as it is or in a cooled condition.

When that material is applied to eyelashes, the result produced is asmooth colored coating which adheres to the eyelash for a long time.

For compositions which were produced as described hereinbefore viscositywas determined as follows:

Measuring apparatus: Bohlin CVOR Rheometer,

Shearing stress ramp 1 to 1000 Pa upwards for recording a flow limit

Measuring system: plate/plate 20 to 0.4 mm gap spacing

Temperature: 25° C.

Measurement Without Pre-Shearing

Measuring time: 120 s plus 60 s pre-heat treatment at 25° C.

Conversion to a viscosity curve is effected electronically

For compositions produced in accordance with the invention, viscositieswere measured under those conditions in the range below 2,500 mPa.s.

1-24. (canceled)
 25. An aqueous-based preparation for application to theskin or skin appendages comprises a mixture of at least two aqueousdispersions of film-forming polymers, wherein one dispersion is apolyurethane-based polymer and the other dispersion is an acrylic-basedpolymer, wherein the preparation has a viscosity in the range of between0.02 and 3.8 Pa·s measured at 25° C. and with 200 s⁻¹.
 26. A preparationas set forth in claim 25, wherein the polyurethane-based polymercomprises at least one polymer is selected from the group consisting ofpolyester polyurethanes, polyether polyurethanes, polyurethane polyvinylpyrrolidones, acrylic polyurethanes, silicone-bearing polyurethanes andmixtures thereof.
 27. A preparation as set forth in claim 25, whereinthe aqueous dispersions form between 50 and 90% by wt. with respect tothe wt. of the final preparation.
 28. A preparation as set forth inclaim 26, wherein the polyurethane-based polymer is present in an amountof between 1 and 60% by wt. with respect to the weight of the finalpreparation.
 29. A preparation as set forth in claim 25, wherein theacrylic-based polymer comprises an acrylic polymer obtained bypolymerization of at least one monomer which contains an ethylenicallyunsaturated bond, selected from the group consisting ofα,β-ethylenically unsaturated carboxylic acids, α,β-ethylenicallyunsaturated carboxylic acid esters, α,β-ethylenically unsaturatedcarboxylic acid amides, and mixtures thereof.
 30. A preparation as setforth in claim 25, wherein the acrylic-based polymer is obtained bypolymerization of monomers selected from the group consisting of acrylicacid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, andmixtures thereof.
 31. A composition as set forth in claim 25, whereinthe acrylic-based polymer is selected from aryl and alkyl acrylates andmixtures thereof.
 32. A preparation as set forth in claim 31, whereinthe acrylic-based polymer comprises a mixture of acrylates copolymer andstyrene/acrylic copolymers.
 33. A preparation as set forth in claim 25,wherein the polymers are present in the dispersions in the form ofparticles of a size of between 10 and 1000 nm.
 34. A preparation as setforth in claim 25, wherein the polymers in the dispersions havefilm-forming temperatures of below 30° C.
 35. A preparation as set forthin claim 25, wherein at least 30% by wt. of the polymers which arecontained in the dispersions are water-resistant in the dried conditionand have a glass transition temperature of below 10° C.
 36. Apreparation as set forth in claim 25, wherein between 5 and 30% by wt.of one or more of the dispersions have a block or portion whose glasstransition temperature in the dried condition is higher than 30° C. 37.A preparation as set forth in claim 25, further comprising, conventionalconstituents selected from the group of plasticisers, wetting agents,anti-foaming agents, coloring agents, preserving agents, fragrances,flavoring agents and mixtures thereof.
 38. A preparation as set forthclaim 30, further comprising at least one pigment.
 39. A preparation asset forth in claim 30, further comprising at least one thickener.
 40. Apreparation as set forth in claim 39, wherein the thickener is selectedfrom the group consisting of natural and/or synthetic and/or modifiedpolysaccharides, mineral and/or modified mineral thickeners, silicatethickeners, celluloses and modified celluloses, non-ionic associativethickeners and/or copolymer thickeners and mixtures thereof.
 41. Apreparation as set forth in claim 25, further comprising at least onepolysaccharide, at least one mineral thickener and at least onevegetable gum.
 42. A preparation as set forth in claim 39, wherein thethickener is selected from the group consisting of cellulose, acellulose derivative, a silicatic thickener, xanthane gum and mixturesthereof.
 43. A preparation as set forth in claim 42, wherein cellulose,silicate and xanthane gum are present in a ratio of between 1:1:4 and1:2:6.
 44. A preparation as set forth in claim 39, wherein the thickeneris present in an amount of between 0.2 and 20% by wt. with respect tothe weight of the final composition.
 45. A preparation as set forth inclaim 39, wherein the thickener is present in an amount of between 0.2and 5% by wt. with respect to the weight of the final composition.
 46. Apreparation as set forth in claim 25, comprising a keratinic material.47. A preparation as set forth in claim 45, for application to hair,eyelashes and/or eyebrows.
 48. A preparation as set forth in claim 45,comprises make up for the eyes and eyelashes.
 49. A device for applyinga preparation as set forth in claim 25, comprise a container which canaccommodate the preparation and which has a neck portion with ascrewthread and a seal, and an applicator element which at its one endhas a brush and at its other end a handle which forms a closure cap,wherein the brush head is of a diameter in the range of between 5.5 and6.5 mm and is of a length in the range of between 12.5 and 17.5 mm andwherein the bristles are arranged in a helical arrangement radiallyaround a central portion with a large number of turns.